RT Journal Article
T1 Gold-catalyzed reaction of propargyl esters and alkynylsilanes: synthesis of vinylallene derivatives through a twofold 1,2- rearrangement
A1 Bernardo, Olaya
A1 González Pelayo, Silvia
A1 Fernández López, Israel
A1 López, Luis A.
AB The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements. Good yields, full atom-economy, broad substrate scope, easy scale-up and low catalyst loadings are salient features of this novel transformation. Density Functional Theory (DFT) calculations suggest a reaction mechanism involving initial [1,2]-acyloxy rearrangement to generate a gold vinylcarbene intermediate which upon regioselective attack of the alkynylsilane affords a vinyl cation which undergoes a type II-dyotropic rearrangement involving the silyl group and the metal fragment. Preliminary results on the enantioselective version of this transformation are also disclosed.
PB Wiley
YR 2021
FD 2021-09-28
LK https://hdl.handle.net/20.500.14352/112664
UL https://hdl.handle.net/20.500.14352/112664
LA eng
NO Bernardo O, González-Pelayo S, Fernández I, López LA. Gold-Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2-Rearrangement. Angew Chem Int Ed Engl. 2021 Nov 22;60(48):25258-25262. doi: 10.1002/anie.202110783. Epub 2021 Oct 21. PMID: 34581473; PMCID: PMC9298039.
NO Ministerio de Ciencia e Innovacin
NO Agencia Estatal de Investigacin
NO Fondo Europeo de Desarrollo Regional
NO Universidad de Oviedo
DS Docta Complutense
RD 18 dic 2025